Although organic polymers have replaced metals in many structural contexts, thus far they have failed to replace metals when the latter are used as electrical conductors or semiconductors. The impetus for such replacement includes, among others, lower cost, lower weight of materials, and increased processing variability for polymers as compared with metals. For example, polymers readily can be cast as films, foils, and fibers by standard, time-tested procedures. Polymers can be formed into a limitless variety of shapes and dimensions by standard processing procedures, thereby adding to the potential benefit of electrically conducting polymers.
A potential use for electrically conducting polymers is as electrodes or components of batteries, where their low weight and possibly unlimited scope of design are attractive. Electrically conducting polymers also could find use in construction of solar cells. Where such polymers are photoconducting they would undoubtedly find applications in the electrophotographic industry.
The conductivity ranges characterizing insulators, semiconductors, and metallic conductors are somewhat arbitrary, but for convenience we may say an insulator has a conductivity less than about 10.sup.-10 ohm.sup.-1 cm.sup.-1, a conducting metal has a conductivity greater than about 10.sup.2 ohm.sup.=1 cm.sup.-1, and a semiconductor has an intermediate conductivity. In some cases organic polymers which are insulators show a sufficient increase in conductivity upon doping to act as semiconductors. By "doping" is meant adding a compound, referred to as a dopant, to the polymer so as to form a redox system wherein an electron is transferred from the polymer to the dopant, or vice versa. Two common examples of dopants are iodine (an electron acceptor) and sodium naphthalide (an electron donor). When the polymer transfers an electron to the dopant to exhibit semiconductor properties it is called a p-type semiconductor because conduction occurs mainly via holes in the valence band. Conversely, when the polymer accepts an electron from the dopant to exhibit semiconductor properties it is called an n-type semiconductor because conduction occurs mainly via electrons in the conduction band.
It is desirable for a normally insulating polymer to become a semiconductor upon doping by both p- and n-type dopants. It is also desirable that the polymer respond to a wide variety of dopants, and for its conductivity to be relatively responsive to changed levels of dopant. It is also desirable that the conductivity properties of the polymer remain stable over time and upon air exposure of the polymer. It is also quite desirable that upon doping the polymer remain flexible rather than becoming brittle.
It is a discovery of this invention that certain condensation polymers of 1,1,2,2-tetrahaloethanes and aromatic diamines, and which have the structure, EQU (.dbd.CH--CH.dbd.N--A--N.dbd.).sub.x
where A is an aromatic moiety selected from the group consisting of benzene, naphthalene, biphenyl, pyridine, and acridine, are polymers which show many of the aforementioned properties. In particular, the polymer from a 1,1,2,2-tetrahaloethane and 1,4-diaminobenzene, poly(ethyleneiminobenzene), hereafter referred to as EIB, is normally an insulator whose conductivity increases to about 10.sup.-4 ohm.sup.-1 cm.sup.-1 upon doping with an electron acceptor such as iodine. In addition to these properties as a p-type semiconductor, EIB can be doped with an electron donor such as sodium naphthalide to behave as an n-type semiconductor. An unexpected and highly advantageous property of EIB after being doped is that some such doped polymers are pliable, in contrast to the brittle character of undoped EIB, thereby facilitating production of shaped electrically conducting polymers.
Polyacetylene and poly(p-phenylene) exemplify some better, perhaps the best, prior art electrically conducting polymers, hence their limitations exemplify the prior art constraints. Although polyacetylene may be doped with p- and n-type dopants, all doped as well as undoped polyacetylene are unstable in air. Thus the electrical properties, which are of greatest interest in this application, are useful for only short periods in air. In contrast, poly(p-phenylene) itself is air stable but it affords air unstable, electrically conducting polymers with both p- and n-type dopants. Moreover, these materials invariably are amorphous powders which cannot be cast, hence their processability is severely limited.